Branched Acid Emulsifier Compositions and Methods of Use

ABSTRACT

Compositions may contain an oleaginous base fluid, and a branched amidoamine surfactant prepared from the reaction of an alkylene amine or an oligoalkylene amine and a branched acid having a C4 to C24 primary hydrocarbon chain, and having one or more C1 to C24 branches. Methods may include emplacing a wellbore fluid into a wellbore, wherein the wellbore fluid contains an oleaginous base fluid; and a branched amidoamine surfactant prepared from the reaction of an alkylene amine or an oligoalkylene amine and a branched acid having a C4 to C24 primary hydrocarbon chain, and having one or more C1 to C24 branches.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Patent Application No.62/273,109 filed on Dec. 30, 2015, which is incorporated herein byreference.

BACKGROUND

During the drilling of a wellbore, various fluids are typically used inthe well for a variety of functions. The fluids may be circulatedthrough a drill pipe and drill bit into the wellbore, and then maysubsequently flow upward through wellbore to the surface. During thiscirculation, the drilling fluid may act to remove drill cuttings fromthe bottom of the hole to the surface, to suspend cuttings and weightingmaterial when circulation is interrupted, to control subsurfacepressures, to maintain the integrity of the wellbore until the wellsection is cased and cemented, to isolate the fluids from thesubterranean formation by providing sufficient hydrostatic pressure toprevent the ingress of formation fluids into the wellbore, to cool andlubricate the drill string and bit, and/or to maximize penetration rate.

SUMMARY

In one or more aspects, embodiments disclosed herein relate tocompositions may contain an oleaginous base fluid, and a branchedamidoamine surfactant prepared from the reaction of an alkylene amine oran oligoalkylene amine and a branched acid having a C4 to C24 primaryhydrocarbon chain, and having one or more C1 to C24 branches.

In another aspect, embodiments disclosed herein relate to methods thatinclude emplacing a wellbore fluid into a wellbore, wherein the wellborefluid contains an oleaginous base fluid; and a branched amidoaminesurfactant prepared from the reaction of an alkylene amine or anoligoalkylene amine and a branched acid having a C4 to C24 primaryhydrocarbon chain, and having one or more C1 to C24 branches.

This summary is provided to introduce a selection of concepts that arefurther described below in the detailed description. This summary is notintended to identify key or essential features of the claimed subjectmatter, nor is it intended to be used as an aid in limiting the scope ofthe claimed subject matter.

DETAILED DESCRIPTION

Embodiments disclosed herein are directed to compositions forstabilizing wellbore fluid formulations, including invert emulsiondrilling and treatment fluids. In another aspect, the present disclosureis directed to amidoamine surfactants prepared from branched acids.Branched amidoamine surfactants in accordance with the presentdisclosure function by stabilizing the interface between oleaginous andaqueous fluids, maintaining the phase boundary between the two phasesand reducing coalescence, settling, and/or creaming.

Branched amidoamine surfactants in accordance with the presentdisclosure may be used to prepare emulsified wellbore fluids, includingwater-in-oil or invert emulsions in which an aqueous internal phase isstabilized by a surfactant in an oil continuous phase. Surfactants, suchas amidoamine surfactants, are relatively small molecules that oftenhave a hydrophobic portion of the molecule that interacts witholeaginous fluids and a hydrophilic, often polar, portion of themolecule that interacts with aqueous fluids. When combined with amixture of aqueous and oleaginous fluids, the surfactant orients at theinterface between the phases and forms a micelle. Depending on thebalance between the hydrophobic and hydrophilic portions of themolecules, surfactants may form stronger barriers between the phases andmore stable emulsions.

In one or more embodiments, branched surfactants may improve thestability of aqueous fluids in invert emulsions by modifying theinterphase packing or the packing efficiency. For example, withsurfactants containing linear hydrocarbons in the hydrophobic portion ofthe molecule, the micelle formed by the surfactant may contain arelatively low surface density of hydrocarbon chains, creating a weakbarrier at the micelle boundary that is more susceptible to rupture andcoalescence of the internal phase during storage or at high-pressure,high-temperature (HPHT) conditions. In contrast, the branched tails ofthe present disclosure may increase the tail's cross-sectional area andthereby provide a more effective packing to protect the micelleinterface.

Branched amidoamine surfactants in accordance with the presentdisclosure may exhibit increased emulsion stability, reduced sag, lowerequivalent circulating density and gel strength than comparative linearamidoamines. Branched amidoamine surfactants may also possess low pourpoints and increased flowability, which translates to easier transportand lower mixing energy requirements during wellbore fluid preparation.Amidoamine surfactants in accordance with the present disclosure mayalso improve the stability of oil-based drilling fluids and invertemulsions, including at HPHT conditions in which standard surfactantsdegrade. Moreover, tuning the branched acid used to prepare theamidoamine surfactants may allow for a systematic approach to surfactantdesign, including tuning emulsion properties to suit a specific mudformulation.

Many of the issues with emulsion instability at HPHT conditions and canbe attributed to several specific issues including insufficientemulsifier hydrolytic stability, incompatibility of the final emulsifiedwellbore fluid with pour point depressants that are often added to aidpourability of the emulsifier, and weak emulsion droplet membranes thatdegrade over time. Amidoamines prepared from branched acids inaccordance with the present disclosure may exhibit enhanced hydrolyticstability, which may be attributed to the increased branching providingsome degree of steric hindrance that lowers the hydrolysis rate of theamide bond between the amidoamine and the branched acid. Moreover,branching may also allow the branched chains to entangle to some degree,which may anchor the emulsifier at the micelle interface.

In addition to surfactant stability, other factors that may beconsidered are the ease of use of surfactant to prepare wellbore fluidcompositions. For example, amidoamine surfactants produced with linearunsaturated fatty acids may also exhibit relatively high pour points,and when temperatures fall below the pour point the surfactant becomes asolid or semi-solid that must be heated in order to transfer thematerial from a storage container. While introducing unsaturation intothe hydrophobic portion of the surfactant may reduce the pour point ofthe surfactant, unsaturation also increases the occurrence of oxidationat these sites, particularly under HPHT conditions. To this end,branched amidoamine surfactants may improve emulsion droplet stabilityand contribute to lowering of the pour point and reduce the need of pourpoint depressants during wellbore fluid preparation that may negativelyaffect emulsion stability or other fluid properties.

In some embodiments, branched amidoamine surfactants may also be used toprepare stable emulsions from oleaginous base fluids such as internalolefins that are becoming more widespread as a “green” alternative todiesel oils. Common emulsifiers often underperform when used withinternal olefin base fluids due to the changes in solvency when comparedwith standard base oils (e.g., diesel). Emulsion stability may befurther hindered by extreme temperature and pressure conditions that candegrade surfactants and other wellbore fluid components. Amidoaminesurfactants may also exhibit favorable environmental and toxicityprofiles when compared to other surfactant classes.

Whether an emulsion of oil and water turns into a “water-in-oil”emulsion or an “oil-in-water” emulsion depends on a number of factorssuch as the volume fraction of both phases, the type(s) of surfactantpresent, temperature, and pH. For most emulsions, the Bancroft ruleapplies, which holds that surfactants tend to produce an internal phasefrom chemicals and solvents in which they are poorly soluble. The degreeof emulsion for a mixed fluid may be tuned from complete emulsion to ametastable emulsion through the selection of the components of thewellbore fluid, particularly by selecting fluid components on the basisof hydrophilic/lipophilic balance (HLB).

HLB refers to the ratio of the hydrophilicity of a surfactant, due tothe presence of polar groups, to the hydrophobicity of the surfactantdue to lipophilic groups. HLB values may be calculated by consideringthe molecular weight contributions of the respective hydrophilic andlipophilic portions and taking the ratio thereof (divided by 5). A HLBvalue of 0 corresponds to a completely hydrophobic molecule, and a valueof 20 corresponds to a completely hydrophilic molecule. Broadly, the HLBvalue may be used to estimate the emulsifying properties of asurfactant. For example, surfactants in the range of 0 to 5 arewater-insoluble and form water-in-oil emulsions, surfactants in therange of 6 to 9 are partially soluble and are often referred to aswetting agents, surfactants in the range of 10 to 12 form translucent toclear solutions in aqueous fluids and referred to as detergents, andsurfactants in the range of 13 to 20 are very water soluble and formoil-in-water emulsions. Branched amidoamine surfactants in accordancewith the present disclosure may have an HLB value within the range of 0to 10 in some embodiments, from 3 to 9 in other embodiments, and from 0to 5 in still other embodiments.

Branched Amidoamine Surfactants

In one or more embodiments, wellbore fluids in accordance with thepresent disclosure may contain one or more branched amidoaminesurfactants prepared from the reaction with an alkylene amine and abranched acid. For example, such branched amidoamine surfactants may berepresented by the chemical formulas (I) to (IV):

where R₁ is a branched alkyl corresponding to the branched hydrocarbonchain contained in branched acid used to produce the amidoaminesurfactant; R², R³, R⁵, and R⁶ are each independently selected from H ora C1 to C4 alkyl; R⁴, R⁷, and R⁸ are each independently selected from H,C1 to C4 alkyl for each carbon, C1 to C4 alkoxyalkyl, C1 to C4hydroxyalkyl, or a hydrophilic capping agent; n and m are integers from1 to 10; and y is an integer from 0 to 5. In some embodiments, alkyleneamines may include oligoalkylene amines prepared from 1 to 5 repeatingunits of a C1 to C10 alkylene amine. The above formulae may be formed byreacting a branched acid with an alkylene amine, and depending on thehydrophilicity of the resulting product, with further optional reactionwith a hydrophilic capping agent, such as a polycarboxylic acid oranhydride.

Branched acids suitable for preparing branched amidoamine surfactantsmay include alkyl carboxylic acids having a C4 to C24 primaryhydrocarbon chain, and having one or more C1 to C24 branches. In otherembodiments, branched acids may include various functionalities in thehydrocarbon chains including alkyl, alkenyl, alkynyl, cyclical, andaromatics.

In some embodiments, branched acids used to produce amidoaminesurfactants in accordance with the present disclosure may containbranched alkyl groups that are symmetrical (having the same carbon chainlength) or nearly symmetrical (the alkyl chains varying in length by oneto three carbons) with respect to the branch point carbon. In someembodiments, amidoamine surfactants may be prepared from carboxylicacids having branching from the alpha carbon adjacent to the carbonylcarbon. For example, amidoamine surfactants of the formulae shown abovemay have an le of the general formula: —(CH₂)_(x)C(R⁹)(R¹⁰)(R¹¹)where R⁹is hydrogen or a C1 to C24 alkyl, R¹⁰ and R¹¹ are C1 to C24 alkyl chainsextending from the branching carbon, where the alkyl chains may be thesame carbon length or different, and x is an integer between 0 and 6. Insome embodiments, amidoamine surfactants may contain an le having aprimary alkyl chain containing one or more alkyl branches from any pointalong the primary carbon chain that may range from C1-C24 in length. Inyet other embodiments, amidoamine surfactants may contain an le havingrepetitive alkyl branching that forms dendrimeric structures.

Amidoamine surfactants in accordance with the present disclosure may beprepared by reacting an alkylene amine or oligoalkylene amine with abranched acid. Branched acids in accordance with the present disclosuremay include, for example, 2-butyloctanoic acid, multiply branched acidssuch as 2,2-dimethyloctanoic acid, 2,2-ethylmethlyheptanoic acid,2,2-methyl-sec-butylbutanoic acid, 2,2-methylethylhexanoic acid,3-ethyl-6-propyl-undecanoic acid, 3,7,11,15-tetramethylhexadecanoicacid, 2,6,10,14-tetramethylpentadecanoic acid, 4,8,12-trimethyldecanoicacid, and the like. In some embodiments, branched acids may includeneoacids such as isooctanoic acid, isononanoic acid, neodecanoic acid,and the like. In one or more embodiments, amidoamine surfactants may beprepared from synthetic branched acids such as ISOCARB™, or branchedacids derived from ISOFOL™, MARLIPAL™, ISALCHEM™, LIAL™, and ALCHEM™,all of which are commercially available from Sasol Chemicals LLC.

As mentioned above and referenced in the above formula, the branchedacid emulsifier may be formed with reaction with a hydrophilic cappingagent. Thus, the hydrophilic capping agent referenced in the aboveformula may include a group formed from reaction of the amine with apolycarboxylic acid, anhydride (of a carboxylic acid such as acetic acidor a polycarboxylic acid, including of those described below such as butnot limited to maleic anhydride and succinic anhydride), urea,isocyanates (such as methylisocyanate), alpha-halocarboxylic acid (suchas chloroacetic acid, chloropropionic acid, etc.), oxirane, cyclicdiesters (such as lactide or glycolide), or cyclic sulfonate ester (suchas propanesultone or other sultones). Polycarboxylic acids may include,for example, lactic acid, glycolic acid and ether derivatives thereof,succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid,oxalic acid, adipic acid, diglycollic acid, tartaric acid, tartronicacid, fumaric acid, citric acid, aconitic acid, citraconic acid,carboxymethyloxysuccinic acid, lactoxysuccinic acid, 2-oxy-1,1,3-propanetricarboxylic acid, oxydisuccinic acid, 1,1,2,2-ethane tetracarboxylicacid, 1,1,3,3-propane tetracarboxylic acid, 1,1,2,3-propanetetracarboxylic acid, cyclopentane-cis, cis, cis-tetracarboxylic acid,cyclopentadienide pentacarboxylic acid, 2,3,4,5-tetrahydrofuran-cis,cis, cis-tetracarboxylic acid, 2,5-tetrahydrofuran-cis-dicarboxylicacid, 1,2,3,4,5,6-hexane-hexacarboxylic acid, mellitic acid,pyromellitic acid, phthalic acid, isophthalic acid, and terphthalicacid. In particular embodiments, the branched acid emulsifier of thepresent disclosure may be represented by formula (V) to(XI):

where R₁ is a branched alkyl corresponding to the branched hydrocarbonchain contained in branched acid used to produce the amidoaminesurfactant; R², R³, R⁵, and R⁶ are each independently selected from H ora C1 to C4 alkyl; R⁷ and R⁸ are each independently selected from H, C1to C4 alkyl for each carbon, C1 to C4 alkoxyalkyl, and C1 to C4hydroxyalkyl; n and m are an integers from 1 to 10; and y is an integerfrom 0 to 5. One of ordinary skill in the art would appreciate thatchemical formulas (V) and (VI) may be arrived at by reacting chemicalformula (I) described above having R⁴ be hydrogen with succinic acid (oranhydride) or maleic acid (or anhydride). Further, chemical formulas(VII) and (VIII) may be arrived at by reacting chemical formula (II)described above having R⁴ be hydrogen with succinic acid (or anhydride)or maleic acid (or anhydride). It is also envisioned that in one or moreother embodiments, R⁴, R⁷ and R⁸ in formulas (I) may each be a hydrogenand reacted with succinic acid (or anhydride) or maleic acid (oranhydride). Thus, the resulting surfactant would be chemical formula (V)or (VI) where R₁ is a branched alkyl corresponding to the branchedhydrocarbon chain contained in branched acid used to produce theamidoamine surfactant; R², R³, R⁵, and R⁶ are each independentlyselected from H or a C1 to C4 alkyl; R⁷ and R⁸ are selected from

n and m are an integers trom 1 to 10; and y is an integer from 0 to 5.In these embodiments (formulae (V) to (X)) containing R⁷ and R⁸, it isunderstood that R⁷ and R⁸ do not need to be formed from reaction withmaleic acid (or anhydride) or succinic acid (or anhydride) but at leastone of R⁷ and R⁸ are formed reaction with maleic acid (or anhydride) orsuccinic acid (or anhydride) if no other amines in the surfactant havebeen so reacted.

Base Fluids

Wellbore fluids in accordance with the present disclosure may beformulated as a water-in-oil or oil-in-water emulsion and, in somecases, a high internal phase ratio (HIPR) emulsion in which the volumefraction of the internal phase is a high as 90 to 95 percent. In someembodiments, wellbore fluids may contain an external oleaginous solventcomponent and an internal aqueous component having a ratio of theinternal aqueous component to the external oleaginous component with therange of 30:70 to 95:5 in some embodiments, from 50:50 to 95:5 in someembodiments, and from 70:30 to 95:5 in yet other embodiments.

Suitable oleaginous fluids that may be used to formulate emulsions mayinclude a natural or synthetic oil and in some embodiments, in someembodiments the oleaginous fluid may be selected from the groupincluding diesel oil; mineral oil; a synthetic oil, such as hydrogenatedand unhydrogenated olefins including polyalpha olefins, linear andbranch olefins and the like, polydiorganosiloxanes, siloxanes, ororganosiloxanes, esters of fatty acids, specifically straight chain,branched and cyclical alkyl ethers of fatty acids, mixtures thereof andsimilar compounds known to one of skill in the art; and mixturesthereof.

Aqueous fluids useful for preparing wellbore fluid formulations inaccordance with the present disclosure may include at least one of freshwater, sea water, brine, mixtures of water and water-soluble organiccompounds, and mixtures thereof. In various embodiments, the aqueousfluid may be a brine, which may include seawater, aqueous solutionswherein the salt concentration is less than that of sea water, oraqueous solutions wherein the salt concentration is greater than that ofsea water. Salts that may be found in seawater include, but are notlimited to, sodium, calcium, aluminum, magnesium, potassium, strontium,and lithium salts of chlorides, bromides, carbonates, iodides,chlorates, bromates, formates, nitrates, oxides, sulfates, silicates,phosphates and fluorides. Salts that may be incorporated in a brineinclude any one or more of those present in natural seawater or anyother organic or inorganic dissolved salts. Additionally, brines thatmay be used in the wellbore fluids disclosed herein may be natural orsynthetic, with synthetic brines tending to be much simpler inconstitution. In one embodiment, the density of the wellbore fluid maybe controlled by increasing the salt concentration in the brine (up tosaturation, for example). In a particular embodiment, a brine mayinclude halide or carboxylate salts of mono- or divalent cations ofmetals, such as cesium, potassium, calcium, zinc, and/or sodium.

In one or more embodiments, branched amidoamine surfactants may produceinvert emulsions having increased stability to temperature and pressureaging, particularly when assayed using electrical stability (ES), forexample. The ES test, specified by the American Petroleum Institute atAPI Recommended Practice 13B-2, Third Edition (February 1998), is oftenused to determine the stability of the emulsion. ES is determined byapplying a voltage-ramped, sinusoidal electrical signal across a probe(consisting of a pair of parallel flat-plate electrodes) immersed in themud. The resulting current remains low until a threshold voltage isreached, whereupon the current rises very rapidly. This thresholdvoltage is referred to as the ES (“the API ES”) of the mud and isdefined as the voltage in peak volts-measured when the current reaches61 μA. The test is performed by inserting the ES probe into a cup of120° F. (48.9° C.) mud applying an increasing voltage (from 0 to 2000volts) across an electrode gap in the probe. The higher the ES voltagemeasured for the fluid, the stronger or harder to break would be theemulsion created with the fluid, and the more stable the emulsion is.Thus, the present disclosure relates to invert emulsion fluids having anelectrical stability of at least 50 V in an embodiment, and in the rangeof 50 V to 1000 V in some embodiments, and from 75 V to 900 V in otherembodiments.

When formulated as an invert emulsion, wellbore fluids may containadditional chemicals depending upon the end use of the fluid so long asthey do not interfere with the functionality of the fluids (particularlythe emulsion when using invert emulsion fluids) described herein. Forexample, weighting agents, wetting agents, organophilic clays,viscosifiers, fluid loss control agents, surfactants, dispersants,interfacial tension reducers, pH buffers, mutual solvents, thinners,thinning agents and cleaning agents may be added to the fluidcompositions of this invention for additional functional properties.

In particular, the wellbore fluids of the present disclosure may beinjected into a work string, flow to bottom of the wellbore, and thenout of the work string and into the annulus between the work string andthe casing or wellbore. This batch of treatment is typically referred toas a “pill.” The pill may be pushed by injection of other wellborefluids such as completion fluids behind the pill to a position withinthe wellbore which is immediately above a portion of the formation wherefluid loss is suspected. Injection of fluids into the wellbore is thenstopped, and fluid loss will then move the pill toward the fluid losslocation. Positioning the pill in a manner such as this is oftenreferred to as “spotting” the pill. Injection of such pills is oftenthrough coiled tubing or by a process known as “bullheading.”

Upon introducing a wellbore fluid of the present disclosure into aborehole, a filtercake may be formed which provides an effective sealinglayer on the walls of the borehole preventing undesired invasion offluid into the formation through which the borehole is drilled. Filtercakes formed from wellbore fluids disclosed herein include multiplelatex polymers and may have unexpected properties. Such properties mayinclude increased pressure blockage, reliability of blockage, andincreased range of formation pore size that can be blocked. Thesefiltercakes may provide filtration control across temperature ranges upto greater than 400° F.

Where the formation is a low permeability formation such as shales orclays, the filtercakes formed using the wellbore fluids and methods ofthe present disclosure prevent wellbore fluid and filtrate loss byeffectively blocking at least some of the pores of the low permeationformation. This may allow for support of the formation by maintainingsufficient pressure differential between the wellbore fluid column andthe pores of the wellbore. Further, the filter cakes formed by wellborefluids of the present disclosure may effectively seal earthenformations, and may be stable at elevated temperatures.

Although a few example embodiments have been described in detail above,those skilled in the art will readily appreciate that many modificationsare possible in the example embodiments without materially departingfrom this disclosure. Accordingly, all such modifications are intendedto be included within the scope of this disclosure as defined in thefollowing claims. In the claims, means-plus-function clauses areintended to cover the structures described herein as performing therecited function and not only structural equivalents, but alsoequivalent structures. Thus, although a nail and a screw may not bestructural equivalents in that a nail employs a cylindrical surface tosecure wooden parts together, whereas a screw employs a helical surface,in the environment of fastening wooden parts, a nail and a screw may beequivalent structures. It is the express intention of the applicant notto invoke 35 U.S.C. § 112(f) for any limitations of any of the claimsherein, except for those in which the claim expressly uses the words‘means for’ together with an associated function.

1. A composition comprising: an oleaginous base fluid; and a branched amidoamine surfactant having at least one C1 to C24 branch, the surfactant prepared from reaction of an alkylene amine or an oligoalkylene amine and a branched acid having a C4 to C24 primary hydrocarbon chain.
 2. The composition of claim 1, wherein the branched amidoamine surfactant is represented by the chemical formulae (I) (II), (III), or (IV):

where R₁ is a branched alkyl corresponding to the branched hydrocarbon chain contained in branched acid used to produce the amidoamine surfactant; R², R³, R⁵, and R⁶ are each independently selected from H or a C1 to C4 alkyl; R⁴, R⁷, and R⁸ are each independently selected from H, C1 to C4 alkyl for each carbon, C1 to C4 alkoxyalkyl, C1 to C4 hydroxyalkyl, and a hydrophilic capping agent; n and m are an integers from 1 to 10; and y is an integer from 0 to
 5. 3. The composition of claim 2, wherein le of the branched amidoamine surfactant is of the formula: —(CH₂)_(x)C(R⁹)(R¹⁰)(R¹¹)where R⁹ is hydrogen or a C1 to C24 alkyl, R¹⁰ and R¹¹ are C1 to C24 alkyl chains extending from the branching carbon, where the alkyl chains may be the same carbon length or different, and x is an integer between 0 and
 6. 4. The composition of claim 3, wherein R¹⁰ and R¹¹ contain the same number of carbons.
 5. The composition of claim 1, further comprising an aqueous internal phase.
 6. The composition of claim 5, wherein the oleaginous base fluid forms an oleaginous external phase, and wherein the composition has a ratio of the aqueous internal phase to the oleaginous external phase with the range of 30:70 to 95:5.
 7. The composition of claim 1, wherein the branched amidoamine surfactant is prepared from a branched acid selected from a group consisting of 2-butyloctanoic acid, 2,2-dimethyloctanoic acid, 2,2-ethylmethlyheptanoic acid, 2,2-methyl-sec-butylbutanoic acid, 2,2-methylethylhexanoic acid, 3-ethyl-6-propyl-undecanoic acid, 3,7,11,15-tetramethylhexadecanoic acid, 2,6,10,14-tetramethylpentadecanoic acid, and 4,8,12-trimethyldecanoic acid.
 8. The composition of claim 1, wherein the hydrophilic capping agent results from reaction with one of a polycarboxylic acid, anhydride, urea, isocyanate, alpha-halocarboxylic acid, oxirane, cyclic diester, or cyclic sulfonate ester.
 9. The composition of claim 8, wherein the branched amidoamine surfactant is selected from chemical formulae (V) to (X):

where R₁ is a branched alkyl corresponding to the branched hydrocarbon chain contained in branched acid used to produce the amidoamine surfactant; R², R³, R⁵, and R⁶ are each independently selected from H or a C1 to C4 alkyl; R⁷ and R⁸ are each independently selected from H, C1 to C4 alkyl for each carbon, C1 to C4 alkoxyalkyl, C1 to C4 hydroxyalkyl and

so long as the branched amidoamine surfactant has at least one group selected from

n and m are an integer from 1 to 10; and y is an integer from 0 to
 5. 10. The composition of claim 1, wherein the branched amidoamine surfactant has a hydrophilic/lipophilic balance (HLB) in the range of 3 to
 9. 11. The composition of claim 1, wherein the branched amidoamine surfactant has an HLB in the range of 0 to
 5. 16-20. (canceled) 